US7700057B2 - Process for the production of titanium products - Google Patents

Process for the production of titanium products Download PDF

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US7700057B2
US7700057B2 US12/083,362 US8336206A US7700057B2 US 7700057 B2 US7700057 B2 US 7700057B2 US 8336206 A US8336206 A US 8336206A US 7700057 B2 US7700057 B2 US 7700057B2
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titanium
solution
double
salt
precipitate
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US20090158895A1 (en
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Asher Vitner
Aharon Eyal
Revital Mali
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Vitner Asher Ltd
Joma International AS
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Joma International AS
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Priority claimed from IL178477A external-priority patent/IL178477A0/en
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Assigned to JOMA INTERNATIONAL AS, ASHER VITNER LTD. reassignment JOMA INTERNATIONAL AS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EYAL, AHARON, MALI, REVITAL, VITNER, ASHER
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/002—Compounds containing, besides titanium, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/008—Titanium- and titanyl sulfate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/14—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention relates to a method for the production of titanium products. More particularly the present invention relates to a method for the production of titanium products from a low-grade-stream solution of titanium.
  • the industrial production of titanium usually includes a chlorination or sulfonation stage, wherein titanium-ores of high-grade are used.
  • HCl/Cl 2 are used to extract titanium from ores and titanium chloride is distilled; thus, a highly purified titanium is produced.
  • the main disadvantage of this process is the high-cost of the titanium-chloride distillation and purification.
  • Titanium dioxide is widely used as a white pigment with a market of about $7 million per year.
  • Titanium oxide being a white pigment is usually produced from high-grade titanium ores.
  • the product has to meet strict standards of content of impurities, particle size and distribution of particle-size.
  • the particle size of the titanium oxide particles ranges from several nanometers to several hundreds of nanometers. The cost of the raw material for the production of these products is high.
  • the process described in the present disclosure enables producing titanium oxide from low-grade titanium stream using a purification stage in which a titanium double salt is produced.
  • Titanium metal is produced from high-grade titanium ores.
  • the product has to meet strict standards of content of impurities.
  • the cost of the raw material for the production of this product is high.
  • Low-grade titanium ores or low grade solution streams obtained from industrial processes are not used for the production of these products.
  • the process described in the present disclosure suggests producing titanium products from low-grade titanium stream using a purification stage in which a titanium double salt is produced.
  • a double salt is defined as a crystal that consists of two different cations and/or anions. Usually it is characterized by a significant lower solubility compared to the simple salts of its components.
  • Patent BR 20012509 authored by SILVA HELIO JOSE in 2003 separates titanium oxide from the other polyvalent cations present in limenite or other titanium containing ores.
  • Fe and Al are separated from the titanium salt prior to the precipitation of Fe(III) in the form of ammonium double salt.
  • ammonium sulfate to a solution obtained by leaching limenite with sulfuric acid, induced the precipitation of the binary salts (NH 4 )Fe(SO 4 ) 2 12H 2 O, (NH 4 ) 2 TiO(SO 4 ) 2 H 2 O, and (NH 4 ) 2 Fe(SO 4 ) 2 6H 2 O together.
  • Double salts can be produced from a large number of polyvalent cations. Both titanium, Fe(III) and Fe(II) produce double salts; and those double salts usually precipitate together.
  • a titanium double salt can be precipitated from a solution containing a high proportion of polyvalent cation and especially Fe(II) and Fe(III) at high yield and high selectivity, to produce a product of a high titanium to polyvalent cations ratio.
  • the crystallization yield is very high while the purity of the double salt is very high. It was also surprisingly found that the produced double salt can be washed with very low losses of titanium, to provide a product of a grade sufficient for the production of titanium metal, raw material for titanium metal and other metal products of high purity and of titanium oxides and titanium salts. This high purity is obtained despite the fact that both Fe(III) and Fe(II) are present in large quantities in the solution and are able to form similar double salts. At higher monovalent cation to anion ratio the iron double salt co-precipitates with the titanium double salt thus reducing the purity of the product.
  • the present invention provides a highly efficient, low-cost purification method, in which low-grade titanium streams are consumed for the production of high-grade titanium, raw materials for the production of high-grade titanium dioxide, high grade titanium metal and other titanium products such as titanyl chloride, titanyl sulfate and other titanium salts.
  • titanium-double-salt refers to a crystal that consists of an anion and two different cations wherein one of said cations is titanium.
  • cation refers to the monovalent cation present in the double salt.
  • anion as used in the present specification refers to the anion present in the double salt.
  • purity or P will be defined as the weight ratio between the titanium to total polyvalent metals, wherein the purity is presented in several cases in terms of percentage, for example, P1 as used in the present specification refers to the purity of titanium feed solution and P2 refers to the purity of the titanium double salt and P3 refers to the purity of the titanium solution (which is the mother liquor formed in the production of the titanium double salt).
  • titanium metal used in the present specification will be referred to in the present disclosure as elementary titanium such as in Titanium sponge or any other titanium metallic product.
  • titanium products used in the present specification refers to various products containing titanium such as titanium hydroxide, titanium oxy hydroxide, titanium chloride, titanium oxy chloride, titanium sulfate, titanium oxysulfate and other titanium organic or inorganic salts
  • said titanium feed might be a low-grade-stream solution of titanium that is formed by leaching titanium ores using an acid solution.
  • said titanium feed comprises an acid selected from the group consisting of acid halides, sulfuric acid, nitric acid or any combination thereof.
  • said feed solution comprises a waste stream from industrial processes and in another embodiment said titanium feed comprises a waste stream from a titanium production process.
  • the present invention thus provides a highly efficient process for the purification of a titanium feed stream and especially from low-grade titanium streams.
  • the present invention further comprises the step of processing said precipitate to produce titanium oxide.
  • titanium oxide products are anatase, rutile and brookite.
  • the present invention further comprises the step of processing said precipitate to produce titanium products other than titanium oxide.
  • Ti(OH) 4 Ti(OH) 4 , TiOCl 2 , TiOCl 2 , TiCl 4 , TiOSO 4 , TiO(NO 3 ) 2 , other titanium inorganic salts, and titanium organic salts.
  • said titanium feed stream is an aqueous waste solution.
  • said titanium feed is formed by leaching titanium ores using an acid solution.
  • the purity of said titanium feed P1 is in the range of between about 10% and about 90%.
  • P1 is lower than 60%.
  • P1 is lower than 50% and in another preferred embodiment P1 is lower than 45%.
  • said titanium feed includes iron with a Fe/Ti ratio of at least 0.25 and the titanium double salt precipitate contains a Fe/Ti ratio of less than 0.02.
  • P1 is less than 70% and P2 is greater than 95%.
  • said titanium feed stream comprises protons and at least one anion selected from the group consisting of halides, sulfate, nitrate and a combination thereof.
  • said titanium feed stream comprises a waste stream from an industrial process.
  • titanium feed stream includes iron and the molar ratio between the iron and titanium in said low-grade stream is in a range of between about 0.2:1 and about 3:1.
  • the molar ratio between titanium and iron in said double salt is greater than the ratio in said feed stream by a factor of at least 5.
  • said cation in said double-salt is ammonium.
  • the cation in said double-salt is selected from the group consisting of sodium and potassium.
  • the anion in said double-salt is selected from the group consisting OH, SO 4 HSO 4 and halides.
  • said precipitate is selected from the group consisting of titanium double salts and titanium basic double salts.
  • said precipitate contains at least 80% of the titanium originally present in said low-grade-stream solution.
  • the ratio P2/P3 is greater than 2.
  • the precipitate contains more than 85% of the titanium present in the titanium feed and the ratio between the polyvalent impurities, i.e. (1-P3)/(1-P2) is greater than 10.
  • the ratio P2/P3 is greater than 10.
  • the temperature of said formed medium is in the range between 0-80° C.
  • the temperature in which said contact is conducted is in the range of 10-50° C.
  • the temperature in which said contact is conducted is in the range of 20-40° C.
  • said titanium solution is modified to form products selected from the group consisting of iron metal, iron oxide and products of other polyvalent cations present in said titanium feed solution, wherein one of the modification stages is crystallization.
  • said iron containing product is selected from the group of iron double salt, iron oxide and iron hydroxide.
  • the anion of said double iron salt is selected from the group consisting of monovalent anions, divalent anions, halide anions, sulfate and bisulfate anions and a combination thereof.
  • the second cation of said double iron salt is selected from the group consisting of ammonium, sodium and potassium.
  • said compound of polyvalent cation is selected from the group consisting of neutral double salts, basic double salt, metal oxides and a metal hydroxide of said polyvalent cation.
  • said method further includes a precipitate washing stage with a solution to form a purified washed precipitate with a purity P4 and a wash solution with a purity of P5, wherein P4>P2>P5.
  • said washing solution comprises the same anion and cation present in the titanium double salt, wherein the cation is selected from the group consisting of ammonium, alkali metals and a combination thereof, and the anion is selected from the group consisting of SO 4 , HSO 4 and halides and a combination thereof, and wherein the concentration of said anion is higher then 15% and the ratio between the concentrations of said cation to said anion in said titanium solution is higher than 0.2 and lower than 1.6.
  • said washing is with a solution comprising protons, ammonium and sulfate ions.
  • the purity of the washed precipitate is higher than 99%.
  • said method further comprises the step of recrystallizing said precipitate, optionally pre-washed, to form a precipitate with a purity of P6 and a mother liquor with a purity P7, wherein P6>P2>P7.
  • the purity of the recrystallized precipitate is higher than 99% and more preferably is higher than 99.9%.
  • said crystallization is induced by an action selected from the group consisting of addition of a monovalent-cation-salt, addition of a monovalent-cation-base, increasing temperature, dilution and a combination thereof.
  • said re-crystallization uses a solution comprising at least one cation and at least one anion selected from the groups thereof mentioned hereinbefore.
  • the method comprises the steps of:
  • the weight ratio between the amount of titanium in said titanium oxide and that in said titanium double-salt is greater than 0.8.
  • said temperature elevation refers to increasing the temperature to be above 80° C.
  • the purity of said titanium-double-salt (P2) is greater than 80%.
  • the purity of said titanium-double-salt (P2) is greater than 85%.
  • the purity of said titanium-double-salt (P2) is greater than 95%.
  • said precipitate includes a production stage of titanium oxide, said method comprising the steps of:
  • said titanium oxide contains at least 70% of the titanium that was present in said titanium feed.
  • the titanium oxide is in the form of nano-particles in the medium range of 5-100 nanometer.
  • the titanium oxide is in the form of nano-particles in the medium range of 100-300 nanometer.
  • the titanium feed is comprising of, among other polyvalent cations also Fe.
  • the residual concentration of ammonium sulfate is above 20% and the residual NH 4 /SO 4 ratio in the titanium solution is in the range of 0.2:1 to 3.1:1 and more preferred in the range of between 0.2:1 and 1.4:1. and most preferred in the range of 0.2:1 to 0.7:1.
  • the formed precipitate is selected from the group consisting of titanium double salts and titanium basic double salts. Especially preferred are embodiments wherein said precipitate contains at least 80% of the titanium that was present in said titanium feed, and most preferably at least 85%.
  • the titanium feed contains a Fe/Ti ratio of at least 0.25 and the titanium double salt precipitate contains Fe/Ti ratio of less than 0.04 and more preferably of less than 0.02.
  • P1 is less than 70% and P2 is greater than 95%.
  • Both Ti(iv), Fe(II) and Fe(III) form double salts and tend to co-precipitate together. Only at the final concentration of the second salt, present in the double salt, wherein the cation is ammonia or alkali and the anion is double salts anion.
  • the titanium double salt is precipitated at high purity.
  • Fe(III) and especially Fe(II) co-precipitate with the Ti double salt. This specific condition enables the precipitation of the titanium double salt at high yield.
  • the precipitation yield increases with increasing the residual second salt concentration and the purity is the highest in the narrow cation/anion ratio range of between 0.2 to 0.8.
  • the purity of the said precipitate, P2 is greater than 80%. In especially preferred embodiments the purity is greater than 90%. and in most preferred is a purity, P2, greater than 95%.
  • the medium comprises sulfate ions wherein the molar ratio between the cation (ammonia or alkali metals) to SO 4 ⁇ is greater than 0.1 and lower than 1.6. According to another preferred embodiment said molar ratio is greater than 0.2 and lower than 1.4, and according to another preferred embodiment, greater than 0.4 and lower than 0.8.
  • the titanium double salt is ammonium titanium sulfate and said third solution used for washing the precipitate comprises protons, ammonia and sulfate at an ammonia to SO 4 ratio of between 0.2 to 1.4.
  • the solution also contains titanium.
  • said solution for dissolving said precipitate comprises a cation that is selected from the group consisting of ammonium and alkali metals and a combination thereof and an anion selected from the group consisting OH, SO 4 , HSO 4 , halides and acid halides and a combination thereof.
  • said solution comprises water.
  • the final anion to cation ratio in the washing solution is between 0.2 to 1.4.
  • the precipitate can be dissolved in water or any other solution, and the salt containing the anion and cation present in the double salt, are added to create a final salt concentration higher than 10% and more preferred, higher than 20%, and most preferred, higher than 30%, and cation to anion ratios of between 0.2 to 1.4.
  • processing said precipitate includes a production stage of titanium chloride, comprising the steps of:
  • the titanium double salt is contacted with a base at a temperature lower than that to precipitate titanic acid.
  • the precipitate is washed and dissolved in acid.
  • the acid is HCl and the product is titanyl chloride.
  • the acid is H 2 SO 4 and the product is titanyl sulfate, and in another preferred embodiment the acid is an organic acid or any inorganic acid.
  • said titanium chloride contains at least 70% of the titanium that was present in said titanium feed solution, and more preferably at least 85%.
  • said titanium chloride or titanyl chloride are further used for the production of titanium metal.
  • the titanium metal is produced from any titanium salt that is produced and more preferably directly from the titanium double salt solution by reduction using the Kroll Process, with Na or Mg as reduction agents, or any other conventional reduction method.
  • the product is elementary titanium such as titanium sponge or titanium ingot or any other elementary titanium product.
  • said titanium solution is modified by crystallization to form products selected from the group consisting of iron metal, iron oxide and products of other polyvalent cations present in said titanium feed.
  • said iron containing product is selected from the group consisting of a double iron salt, iron oxide and iron hydroxide.
  • the anion comprising said double iron salt is selected from the group consisting of monovalent anions, divalent anions, halide anions, sulfate and bisulfate anions and a combination thereof.
  • the second cation of said double-iron-salt is selected from the group consisting of ammonium, sodium and potassium.
  • said second solution is modified by a crystallization stage to form products of other polyvalent cations present in said titanium feed selected from the group consisting of neutral double salts of their cation, basic double salts, metal oxides or metal hydroxides of their cation.
  • said crystallization stage is induced by a step selected from the group consisting of addition of a monovalent-cation-salt, addition of a monovalent-cation-base, increasing temperature, dilution and a combination thereof.
  • the ratio between the total titanium amount in said titanium metal or titanium chloride is greater than 0.8 of the initial amount of titanium and more preferably greater then 0.95.
  • said reduction methods refers to increasing the temperature to be above 80° C.
  • said temperature elevation refers to increasing the temperature to be above 200° C. and most preferred is increasing the temperature to be above 250° C.
  • FIGS. 1-3 present flow diagrams of embodiments of the present invention.
  • FIG. 1 presents a flow diagram of one of the preferred processes according to the embodiments of the present invention.
  • titanium ores are leached using an acid solution to form a titanium feed solution of titanium salt, wherein the acid is selected from the group is consisting of acid halides, sulfuric acid, nitric acid or any combination thereof.
  • the acid in the present figure was chosen to be sulfuric acid.
  • Two streams are exiting the leaching stage: a waste stream that contains undissolved solids and a stream defined as the titanium feed, which is entering Stage 2—the precipitation stage.
  • a waste stream from a titanium production process, or a waste stream from an iron production process is introduced at Stage 2 to the precipitation stage.
  • Stage 2 said medium is formed by mixing the titanium feed with a reagent selected from the group consisting of an anion and a monovalent cation, wherein the cation of the salt is selected from the group consisting of ammonium and alkali metals and a combination thereof, and the anion salt is selected from the group consisting of OH, SO 4 , HSO 4 , halides and a combination thereof, to form a titanium double-salt which precipitates and a mother liquor that is referred here as titanium solution.
  • a reagent selected from the group consisting of an anion and a monovalent cation, wherein the cation of the salt is selected from the group consisting of ammonium and alkali metals and a combination thereof, and the anion salt is selected from the group consisting of OH, SO 4 , HSO 4 , halides and a combination thereof, to form a titanium double-salt which precipitates and a mother liquor that is referred here as titanium solution.
  • FIG. 1 demonstrates the addition of a solution containing (NH 4 ) 2 SO 4 to Stage 2.
  • this stage is conducted at a temperature range of 0-80° C., and in another preferred embodiment this stage is conducted at a temperature range of 10-50° C. and in yet another preferred embodiment, in the range of 20-40° C.
  • Two streams are exiting the Precipitation stage: the formed titanium double-salt, which precipitates, and titanium solution.
  • the molar ratio between the ammonia and the SO 4 ⁇ in the mother liquor is greater than 0.1. In another preferred embodiment it is greater than 0.2 and lower than 1.4 and in another preferred embodiment it is greater than 0.4 and lower than 0.8.
  • the second cation in said titanium-double-salt is ammonium, while yet in another preferred embodiment it is selected from the group consisting of sodium, potassium or any alkaline metal.
  • the said titanium-double-salt comprises at least 80% of the titanium that was presented in said titanium feed, and more preferably at least 85%.
  • this stage is characterized by the formation of a very pure titanium-double-salt wherein its purity (P2) is greater than 80%, preferably greater than 85%, more preferably greater then 90% and in the most preferred embodiment It is greater then 95%, wherein the ratio P2/P3 is greater than 2, more preferably greater than 5 and most preferably greater than 10.
  • Two streams are exiting the precipitation stage: the formed titanium double-salt, which precipitates, and a solution which is entering Stage 5.
  • At least a portion of the formed titanium double-salt which precipitates in Stage 2 is separating from said solution and enters Stage 3 for a washing stage.
  • the double-salt is washed with a third solution to form a purified precipitate of titanium salt with titanium purity of P4 and a wash solution with a titanium purity of P5, wherein P4>P2>P5.
  • the third solution comprises the same cation and anion used in the precipitation stage (Stage 2).
  • this solution contains NH 4 HSO 4 and H 2 SO 4 , wherein in a more specific preferred embodiment the SO 4 /HSO 4 molar ratio in said solution is smaller then 2.
  • FIG. 1 shows that said third solution is a recycled stream exiting from Stage 4.
  • said wash solution is exiting the washing stage and a portion of it is recycling back to Stage 2 with the addition of NH 4 OH and another portion of it is recycling back to the leaching stage, Stage 1, with the addition of H 2 SO 4 .
  • the titanium double-salt precipitate is then entered into the dissolution and re-precipitation stages (Stage 4) to form purified titanium salt precipitate with a titanium purity of P6 and a second wash solution with a titanium purity P7, wherein P6>P2>P7.
  • the solution in this stage comprises the same cation and anion used in Stage 2.
  • said solution comprises NH 4 HSO 4 and H 2 SO 4 which is recycled back to Stage 3.
  • said solution is water.
  • the recrystallization stage is induced by a step selected from the group consisting of dilution, heating, increasing pH or a combination thereof.
  • the titanium product exiting the recrystallization stage contains at least 70% of the titanium that was present in said low-grade-source solution, more preferably at least 85%.
  • the titanium product is titanium chloride or titanyl chloride of a purity sufficient to produce titanium metal.
  • the said second solution exiting Stage 2 is modified to form products selected from the group consisting of iron metal, iron oxide and products of other polyvalent cation presented in the low-grade-source of titanium feed.
  • FIG. 2 presents a flow diagram of one of the preferred processes according to the embodiments of the present invention. This figure is very similar to FIG. 1 , however, instead of a Washing stage of the titanium-double salt (Stage 3) this figure presents Dissolution and Re-Crystallization steps for the final purification of the titanium-double-salt.
  • FIG. 3 presents a flow diagram of one of the preferred processes according to the present invention for a method of the production of a titanium metal from titanium double-salt solution, comprising the steps of dissolution of a titanium double-salt in solution and inducing the conditions to distill titanium chloride from said solution.
  • the anion titanium double salt is chloride and the titanium chloride is distilled out from the salt as is or after the addition of water or/and solvent.
  • the anion titanium double salt is sulfate and the titanium chloride or titanyl chloride are produced by the addition of chloride salt or HCl and water and/or solvent.
  • the titanium double salt is reduced by the Kroll process to produce elementary titanium.
  • Stage 1 presents dissolution of a titanium double-salt in an aqueous solution.
  • this stream in this figure was noted to be water.
  • the example teaches us that Fe cations and titanium cations co-precipitate as double salts at low residual titanium and Fe concentrations or low residual ammonium sulfate concentrations to form un-pure double salt
  • the example teaches us that precipitation of titanium salt of high purity can be obtained even from solution in which the residual Fe concentration is much higher than that of the Ti
  • Example 5.2 2.0 gr double salt obtained in Example 5.2 were dissolved in 10 gr water. The solution was heated to 169° C. A precipitate was formed. The concentration of Ti in the remaining solution was about 0.05%
  • Example 5.1 2.0 gr double salt obtained in Example 5.1 were dissolved in 2 gr water. 0.2M NaOH solution was added slowly to pH of 4.2. A precipitate was formed. The precipitate was separated and washed and found to be titanic acid.
  • Example 5.2 2.0 gr double salt obtained in Example 5.2 were dissolved in 2 gr water. 0.2M NaOH solution was added slowly to pH of 4.2. A precipitate was formed. The precipitate was separated and washed and found to be titanic acid.
  • Example 5.2 2.0 gr double salt obtained in Example 5.2 were dissolved in 2 gr water. 0.2M NaOH solution was added slowly to pH of 4.2. A precipitate was formed. The precipitate was separated and washed and found to be titanic acid. The precipitate is washed with propanol.
  • Example 5.2 2.0 gr double salt obtained in Example 5.2 were dissolved in 2 gr water. 0.2M NaOH solution was added slowly to pH of 4.2. A precipitate was formed. The precipitate was separated and washed and found to be titanic acid.
  • Lauryl sulfonate solution was added to the solution to form an organic titanyl salt.

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US12/083,362 2005-10-11 2006-10-15 Process for the production of titanium products Active US7700057B2 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
IL17136305A IL171363A (en) 2005-10-11 2005-10-11 Process for producing titanium oxide
IL17136405 2005-10-11
IL171363 2005-10-11
IL171364 2005-10-11
IL178477 2006-10-05
IL178477A IL178477A0 (en) 2006-10-05 2006-10-05 A process for the production of titanium products
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US8628736B2 (en) * 2007-06-28 2014-01-14 Asher Vitner Ltd. Process for the production of titanium salts
US7682303B2 (en) 2007-10-02 2010-03-23 Sonitus Medical, Inc. Methods and apparatus for transmitting vibrations
CA2776368C (en) 2009-10-02 2014-04-22 Sonitus Medical, Inc. Intraoral appliance for sound transmission via bone conduction
CN102146523B (zh) * 2011-03-03 2012-10-10 东北大学 一种用钛铁矿制备二氧化钛和氧化铁的方法

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US2098056A (en) * 1936-02-15 1937-11-02 Du Pont Utilization of waste products in the manufacture of titanium compounds from titanium ores
US2345980A (en) * 1939-09-22 1944-04-04 Du Pont Production of titanium pigments
US2521392A (en) * 1948-10-14 1950-09-05 Nat Lead Co Method for the preparation of titanium dioxide
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US20090158895A1 (en) 2009-06-25
MX2008004728A (es) 2008-09-09
AU2006300754B2 (en) 2012-09-20
PL1957408T3 (pl) 2011-09-30
EP1957408B1 (en) 2011-01-26
EA014448B1 (ru) 2010-12-30
NO20081773L (no) 2008-04-30
BRPI0617302A2 (pt) 2011-07-19
EP1957408A1 (en) 2008-08-20
JP5102770B2 (ja) 2012-12-19
DE602006019903D1 (de) 2011-03-10
SI1957408T1 (sl) 2011-11-30
WO2007043055A1 (en) 2007-04-19
JP2009511413A (ja) 2009-03-19
AP2008004462A0 (en) 2008-06-30
EA200800804A1 (ru) 2008-10-30
KR20080072645A (ko) 2008-08-06
AU2006300754A1 (en) 2007-04-19
ATE496871T1 (de) 2011-02-15

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